EP0273090A1 - Lösungspolymerisation von Acrylsäuremonomerderivaten durch Verwendung von Tertioalkyl(C5)-Hydroperoxiden - Google Patents

Lösungspolymerisation von Acrylsäuremonomerderivaten durch Verwendung von Tertioalkyl(C5)-Hydroperoxiden Download PDF

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Publication number
EP0273090A1
EP0273090A1 EP87100025A EP87100025A EP0273090A1 EP 0273090 A1 EP0273090 A1 EP 0273090A1 EP 87100025 A EP87100025 A EP 87100025A EP 87100025 A EP87100025 A EP 87100025A EP 0273090 A1 EP0273090 A1 EP 0273090A1
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EP
European Patent Office
Prior art keywords
carbons
tertiary
methacrylate
alkyl
monomer
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Granted
Application number
EP87100025A
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English (en)
French (fr)
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EP0273090B1 (de
Inventor
Vasanth R. Kamath
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema Inc
Original Assignee
Pennwalt Corp
Atochem North America Inc
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Priority to JP61309006A priority Critical patent/JPS63168415A/ja
Application filed by Pennwalt Corp, Atochem North America Inc filed Critical Pennwalt Corp
Priority to DE8787100025T priority patent/DE3777581D1/de
Priority to EP87100025A priority patent/EP0273090B1/de
Priority to AT87100025T priority patent/ATE73826T1/de
Priority to ES198787100025T priority patent/ES2030001T3/es
Publication of EP0273090A1 publication Critical patent/EP0273090A1/de
Application granted granted Critical
Publication of EP0273090B1 publication Critical patent/EP0273090B1/de
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C08F2/06—Organic solvent

Definitions

  • This invention relates to an improved process for polymerizing monomers derived from substituted or unsubstituted acrylic acid/methacrylic acid and esters thereof using an initiating amount of a tertiary alkyl hydroperoxide having at least five carbons and/or its derivatives wherein the polymer product has a low molecular weight and a narrow molecular weight distribution suitable for high solids coating applications.
  • Free radical solution polymerization is the most widely used commercial process for the preparation of polymers suitable for use in high solid coating formulations.
  • Azonitrile compounds espectially symmetrical azonitrile compounds, are currently being used as the free radical source in the industry for producing polymers suitable as high solids coating resins by solution polymerization technique.
  • Azonitrile initiators generally produce much narrower MWD polymers in comparison to conventional organic perioxide initiators. (Conventional organic peroxides are primarily derivatives of tertiary butyl hydroperoxides). By the ability of the azonitrile compounds to produce narrow MWD polymers, this makes azonitrile compounds preferred initiators for high solid coating resin production.
  • tertiary alkyl perioxide having at least five carbon atoms are known in the prior art, no publication was found which discloses the use of these perioxides for producing polymers having a narrow molecular weight distribution which polymers will be suitable in high solids coating formulations.
  • U.S. Patent Nos. 3,686,102, 3,950,432, and 4,137,105 discloses the use of tertiary amyl(C 5 ) and tertiary octyl (C a ) peroxides as free radical initiators for vinyl polymerization.
  • U.S. Patent No. 4,130,700 discloses the use of tertiary amyl diperoxyketals as finishing catalysts to reduce residual styrene levels for the bulk polymerization of styrene.
  • the present invention is directed to an improved process for the production of polymers suitable for high solids coating applications.
  • This process comprises solution polymerizing monomers derived from substituted or unsubstituted acrylic acid or methacrylic acid or esters thereof wherein 20-40% by weight of the monomer composition is hydroxyalkyl acrylate or methacrylate in a temperature range of from about 90° to 200°C in the presence of a solvent suitable for high solids coating applications wherein the solvent to monomer ratio is 3:1 to 0.1:1, and in the presence of an initiating amount of tertiary alkyl hydroperoxide and/or its derivatives having a one hour half-life temperature in the range of 50°-190°C and having at least five carbons in the tertiary alkyl component.
  • the derivatives of the hydroperoxide are selected from peroxyketals, dialkylperoxides, peroxyesters, and monoperoxycarbonates.
  • the initiator and monomers, alone or in combination, are added continuously at a programmed rate wherein the rate of addition corresponds approximately to the rate of decomposition of said monomer and initiator over a period of at least about 3 hours so that at the end of the addition the percent conversion of monomer to polymer is at least about 90-95%.
  • the polymer product has a narrow MWD and an average molecular weight of 4000 or less.
  • POlymers suitable for high solids coating applications are prepared by solution polymerization in which select monomers are blended with solvent, polymerization initiator(s), and, optionally, a chain transfer agent, and heated to about 90°-200°C for 1-10 hours.
  • Low solvent to monomer (s/m) ratios are used to conduct the polymerization in order to achieve the desired high solids content required for high solids coating applications, typically, 25 to 90% solids by weight.
  • the solvent to monomer ratios generally used are in the range of (3/1) to (0.1/1).
  • the polymer's molecular weight has to be very low.
  • the normal number-average molecular weight ( M n ) is of the order of 4000 or less.
  • a preferred method for preparing the low molecular weight polymers suitable for high solids coating applications is a programmed addition of monomers and initiator(s) at a given rate into a polymerization vessel containing solvent at the desired temperature and/or refluxing temperature.
  • Monomer(s) and initiator-(s), along or in combination, are metered into reaction solvent at a rate such that the addition time is about 1-12 hours, preferably 3-10 hours.
  • the rate of addition of the two can be the same or different. In general, the rate of initiator and monomer addition is adjusted/controlled to be about equal to the rate of consumption/polymerization in the reaction medium.
  • the rate of addition of initiator and monomer By controlling the rate of addition of initiator and monomer to correspond approximately to the rate of decomposition so that there is no build up in the reactor, drift in the polmer product molecular weight with percent conversion is substantially eliminated.
  • the percent conversion of monomer to polymer attainable is about 90-95% or better.
  • the percent residual monomer(s) at the end of the monomer / initiator addition is generally about 1.0% or higher.
  • Polymerization is generally conducted at about the reflux temperature of the solvent or mixture of solvents.
  • the initiator would preferably have a half-life of about 1-60 minutes, preferably 5-20 minutes, at the polymerization temperature.
  • tertiary-alkyl (? C 5 ) hydroperoxide derivatives as chaser catalysts.
  • the chaser catalyst employed can be the same or different as the one used in conducting the polymerization.
  • the use of the tertiary-alkyl (a C 5 ) hydroperoxide derivatives of the present invention as chaser catalysts results in a reduction in the percent residual monomer(s) to 0.1% and less without any adverse effects on polymer molecular weight and MWD.
  • a high solids coatings resin other than low molecular weight, is it must contain chemically active groups (usually hydroxyl or carboxy functionality) in order to undergo molecular weight buildup and network formation during the final crosslinking (curing) reaction where compounds such as melamine are used as the curing agents.
  • chemically active groups usually hydroxyl or carboxy functionality
  • Polymers suitable for use in high solids coating formulations normally, have a hydroxyl content of from about 2 to about 7% weight.
  • a sufficient amount of hydroxyalkyl acrylate or methacrylate is used (normally, 20-40% by weight of the monomer composition).
  • hydroxyalkyl acrylates and methacrylates that can be used to prepare polymers suitable for high solids coating applications include: 2-hyrdroxyethyl acrylate, 2-hyrdroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hyrdroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2 hydroxybutyl methacrylate, 3 hydroxypropyl acrylate, 4-hydroxybutyl acrylate, and the like.
  • alkyl acrylates and methacrylates that can be used to prepare polymers suitable for high solids coating applications include: methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, buyl acrylate, isobutyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, and the like.
  • Adhesion promoting monomers can also be used in the preparation of polymers suitable for high solids coating applications, such as diethylaminoethyl methacrylate, di-methylaminoethyl methacrylate, tertiary- butylaminoethyl methacrylate, 3-(2-methacryloxyethyl)-2,2-spirocyclohexyl oxazolidene, and the like.
  • the primary considerations in the selection of a suitable solvent are cost, toxicity, flammability, volatility, and chain-transfer activity.
  • An Example of a polymer suitable for high solids coating applications contains 30 % by weight methyl methacrylate, 40% by weight isobutyl methacrylate, and 30% by weight hydroxyethyl methacrylate.
  • Other useful polymers would comprise about 10-30% by weight styrene, 30-60% by weight butyl methacrylate and / or acrylate, and 20-40% by weight hydroxyethyl methacrylate and/or acrylate; the polymer should have a number-average molecular weight ( M n ) of the order of 4,000 or less.
  • molecular weights and MWD of polymers can be measured by many different methods (e.g., vapor phase osmometry, ultracentrifugation, and light scattering), the method used in the practice of this invention (gel permeation chromatography) is particularly preferred.
  • Gel permeation chromatography GPC is the most widely used method within the polymer industry to measure the molecular weights and MWD of polymers.
  • the tertiary-alkyl (Z C 5 ) peroxide initiators used in the practice of this invention are those that have one hour half-life temperatures in the range of 50° to 190°C., preferably those in the range of 60° to 170°C. (half-life is defined as the time it takes for one half of a given quantity of peroxide in dilute solution (i.e., typically, 0.2 molar in a solvent such as dodecane or toluene) to decompose).
  • the initiator concentration used in the practice of this invention is in the range of about 0.50 to about 10.0 parts by weight per 100 parts of monomer, preferably about 2.0 to about 5.0 parts by weight per 100 parts of monomer.
  • High initiator concentration facilitates the production of the desired low molecular weight polymer.
  • high initiator concentration facilitates the production of the desired narrow MWD.
  • a mixture of two or more tertiary-alkyl ( ⁇ C 5 ) peroxides can also be used in the practice of this invention.
  • tertiary-alkyl ( ⁇ C 5 )VRK hydroperoxides and/or derivatives of said hydroperoxides employed in the practice of this invention as polymerization initiators are of the formula:
  • Suitable tertiary-alkyl ( ⁇ C 5 ) peroxide initiators used in the practice of this invention include:
  • This example illustrates the performance of conventional tertiary-butyl peroxides in comparison to peroxides derived from tertiary-alkyl hydroperoxide with five carbons (i.e. tertiary-amyl peroxides) with respect to polymer molecular weight, MWD, and polymer solution color.
  • This example illustrates the performance of conventional tertiary-butyl peroxides in comparison to peroxides derived from tertiary-alkyl hydroperoxide with eight carbons (i.e. tertiary-octyl peroxides) with respect to polymer molecular weight and distribution (MWD).
  • This example illustrates the performance of azonitrile initiators (VazoO) versus the preferred teritary- alkyl peroxide initiators of the present invention (i.e. tertiary-amyl peroxyketals) with respect to polymer molecular weight, MWD, and polymer solution color.
  • VazoO azonitrile initiators
  • tertiary-amyl peroxyketals preferred teritary- alkyl peroxide initiators of the present invention
  • This example illustrates the performance of an azonitrile initiator (i.e. Vazo@-88) versus an initiator of the present invention with respect to polymer molecular weight, MWD, percent conversion, and solution color.
  • Vazo@-88 azonitrile initiator
  • the same percent conversion was obtained in less time (5 hrs. vs. 6 hrs.) with the initiator of the present invention vs. the azonitrile initiator. Also, lower molecular weight, narrower MWD, and lower solution color was obtained with Lupersol@533 vs. Vazo@-88 while employing a low solvent to monomer ratio. Thus, for conducting polymerizations at low solvent to monomer ratios, preferred initiators of the present initiator, specifically Lupersol@533 would be favored over azonitrile initiators.
  • This example illustrates the relative performance of a conventional tertiary butyl peroxide and its corresponding tertiary-alkyl (>C 5 ) analog with respect to polymer molecular weight, MWD, and solution viscosity at a low solvent to monomer ratio.
  • the initiators were compared on an equal molar basis, after correcting for any assay differences.
  • oxo-heptyl acetate solvent 150 g was heated to the specified reaction temperature (See Table 7) in a jacketed glass reactor equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas sparging line.
  • a mixture of (a) 180 g styrene, (b) 180 g BA, (c) 120 g BMA, (d) 120 g HEA, and (e) initiator was added uniformly at a rate of 100 g per hour to the solvent for five hours. After the monomer/initiator addition was completed, polymerization was continued for one-half hour. At the end of five and one-half hours an additional charge of initiator was added (i.e. chaser) and polymerization was further continued for one hour.
  • the percent solids (polymer) content was determined based on a gas chromatographic analysis of percent residual monomer(s) and solvent content by weight present in solution after polymerization.
  • Polymer solution viscosity at ambient temperature was determined using a Brookfield viscometer model #HBT with a spindle #HB2 at a speed of 10 rpm.
  • This example illustrates the performance of a mixture of a conventional t-butyl peroxide and a tertiary-alkyl (>C 5 ) peroxide initiator with respect to polymer molecular weight and MWD.
  • a tertiary-alkyl ( ⁇ C 5 ) peroxide would represent a slightly higher cost product than a t-butyl peroxide.
  • This example illustrates the performance of tertiary-alkyl ( ⁇ C 5 ) peroxide initiators with respect to polymer molecular weight and MWD using various monomer combinations.
  • This example compares the molecular weight and MWD of suitable high solids coating resins prepared using initiators of the present invention to a commercial high solids acrylic resin (i.e., Acryloid® AT-400, Rohm & Haas) currently being used by the industry.
  • a commercial high solids acrylic resin i.e., Acryloid® AT-400, Rohm & Haas
  • the molecular weight and MWD of the resins were determined as described in Example 1.
  • suitable coating resins prepared using initiators of the present invention possess a significantly narrower MWD, particularly the M z/ M n ratio, than commercially used high solids acrylic resins (i.e. Acryloid® AT-400).
  • the narrower MWD resins obtained with initiators of the present invention would allow one to go to higher solids contents without substantially affecting the solution viscosity. Also, the narrower MWD resins would result in achieving superior film properties as previously discussed in the present invention.
  • This example illustrates the performance of conventional tertiary-butyl peroxides in comparison to peroxides derived from tertiary-alkyl hydroperoxide with five carbons (i.e., tertiary-amyl peroxides) as chaser catalysts (i.e., ability to reduce residual monomer without altering M n and MWD of polymer) for solution acrylic resins.
  • Initiators were compared on an equal molar basis after correcting for any assay differences at a temperature corresponding to the 15 minute half-life of the initiator.
  • Percent residual monomers were determined by gas chromatography.
  • Resin molecular weight and distribution were determined by GPC analysis (See Example 1).
  • tertiary-alkyl (C 5 ) peroxides would be preferred over their conventional t-butyl analogs as chaser catalysts for solution acrylic resins.
  • the use of the tertiary-amyl (C 5 ) peroxide resulted in a reduction in residual monomer without significantly altering the molecular weight and distribution of the resin.
  • the use of the tertiary-butyl peroxide resulted in an increase (broadening) of the distribution (MWD) of the resin.
  • a chaser catalyst reduce the residual monomer level (i.e., for health toxicity concerns) without altering the molecular weight and distribution of ther resin (i.e., without increasing the solution viscosity of the resin solution).
  • initiators of the present invention would be desirable as chaser catalysts.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
  • Polymerization Catalysts (AREA)
  • Paints Or Removers (AREA)
EP87100025A 1987-01-02 1987-01-02 Lösungspolymerisation von Acrylsäuremonomerderivaten durch Verwendung von Tertioalkyl(C5)-Hydroperoxiden Expired EP0273090B1 (de)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP61309006A JPS63168415A (ja) 1987-01-02 1986-12-26 ｔ−アルキルヒドロペルオキシドを用いたアクリル酸誘導体モノマ−の溶液重合方法
DE8787100025T DE3777581D1 (de) 1987-01-02 1987-01-02 Loesungspolymerisation von acrylsaeuremonomerderivaten durch verwendung von tertioalkyl(c5)-hydroperoxiden.
EP87100025A EP0273090B1 (de) 1987-01-02 1987-01-02 Lösungspolymerisation von Acrylsäuremonomerderivaten durch Verwendung von Tertioalkyl(C5)-Hydroperoxiden
AT87100025T ATE73826T1 (de) 1987-01-02 1987-01-02 Loesungspolymerisation von acrylsaeuremonomerderivaten durch verwendung von tertioalkyl(c5)-hydroperoxiden.
ES198787100025T ES2030001T3 (es) 1987-01-02 1987-01-02 Polimerizacion en solucion de monomeros derivados de acido acrilico utilizando hidroperoxidos de alquilo terciario (c5).

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP87100025A EP0273090B1 (de) 1987-01-02 1987-01-02 Lösungspolymerisation von Acrylsäuremonomerderivaten durch Verwendung von Tertioalkyl(C5)-Hydroperoxiden

Publications (2)

Publication Number Publication Date
EP0273090A1 true EP0273090A1 (de) 1988-07-06
EP0273090B1 EP0273090B1 (de) 1992-03-18

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EP87100025A Expired EP0273090B1 (de) 1987-01-02 1987-01-02 Lösungspolymerisation von Acrylsäuremonomerderivaten durch Verwendung von Tertioalkyl(C5)-Hydroperoxiden

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EP (1) EP0273090B1 (de)
JP (1) JPS63168415A (de)
AT (1) ATE73826T1 (de)
DE (1) DE3777581D1 (de)
ES (1) ES2030001T3 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010008678A (ko) * 1999-07-02 2001-02-05 신재섭 좁은 분자량분포를 가지는 올레핀계 저분자 중합체의 정밀한 분자량조절방법
WO2012107689A1 (fr) 2011-02-10 2012-08-16 Arkema France Polymerisation radicalaire de l'ethylene amorcee par des peroxydes organiques a haute productivite

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3357100B2 (ja) * 1992-12-01 2002-12-16 積水化学工業株式会社 アクリル系粘着剤の製造方法
DE4324801A1 (de) * 1993-07-23 1995-01-26 Hoechst Ag Verfahren zur Herstellung von OH-Gruppen enthaltenden Copolymerisaten und deren Verwendung in festkörperreichen Beschichtungsmitteln
JP4774172B2 (ja) * 2001-08-23 2011-09-14 化薬アクゾ株式会社 アクリル樹脂の製造方法
FR3041645B1 (fr) * 2015-09-29 2017-09-08 Arkema France Polymerisation radicalaire de l'ethylene amorcee par un couple de peroxydes organiques a haute productivite
TWI751145B (zh) * 2016-03-18 2022-01-01 日商日油股份有限公司 (甲基)丙烯酸酯系塗料用清漆之製造方法
JP6868979B2 (ja) * 2016-07-06 2021-05-12 株式会社日本触媒 アクリル酸エステル重合体およびその製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3832336A (en) * 1970-06-03 1974-08-27 Pennwalt Corp Curing and polymerizing processes employing beta-substituted diperoxyketals
AT367436B (de) * 1980-11-13 1982-07-12 Vianova Kunstharz Ag Verfahren zur herstellung von copolymerisaten
US4369299A (en) * 1977-11-11 1983-01-18 Asahi Kasei Kogyo Kabushiki Kaisha Acrylic resin having excellent solvent resistance and moldability
EP0136813A2 (de) * 1983-09-06 1985-04-10 Exxon Research And Engineering Company Copolymerisation von ungesättigten Estern
EP0136439A2 (de) * 1983-07-25 1985-04-10 The B.F. GOODRICH Company Acryl-Polymere mit mittlerem Molekulargewicht

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3832336A (en) * 1970-06-03 1974-08-27 Pennwalt Corp Curing and polymerizing processes employing beta-substituted diperoxyketals
US4369299A (en) * 1977-11-11 1983-01-18 Asahi Kasei Kogyo Kabushiki Kaisha Acrylic resin having excellent solvent resistance and moldability
AT367436B (de) * 1980-11-13 1982-07-12 Vianova Kunstharz Ag Verfahren zur herstellung von copolymerisaten
EP0136439A2 (de) * 1983-07-25 1985-04-10 The B.F. GOODRICH Company Acryl-Polymere mit mittlerem Molekulargewicht
EP0136813A2 (de) * 1983-09-06 1985-04-10 Exxon Research And Engineering Company Copolymerisation von ungesättigten Estern

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 97, no. 16, October 1982, page 91, abstract no. 129218j, Columbus, Ohio, US; & AT-B-367 436 (VIANOVA KUNSTHARZ AG) 12-07-1982 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010008678A (ko) * 1999-07-02 2001-02-05 신재섭 좁은 분자량분포를 가지는 올레핀계 저분자 중합체의 정밀한 분자량조절방법
WO2012107689A1 (fr) 2011-02-10 2012-08-16 Arkema France Polymerisation radicalaire de l'ethylene amorcee par des peroxydes organiques a haute productivite
FR2971510A1 (fr) * 2011-02-10 2012-08-17 Arkema France Polymerisation radicalaire de l'ethylene amorcee par des peroxydes organiques a haute productivite
US9045571B2 (en) 2011-02-10 2015-06-02 Arkema France Free radical polymerisation of ethylene initiated by organic peroxides with high productivity

Also Published As

Publication number Publication date
ATE73826T1 (de) 1992-04-15
ES2030001T3 (es) 1992-10-16
EP0273090B1 (de) 1992-03-18
JPS63168415A (ja) 1988-07-12
DE3777581D1 (de) 1992-04-23

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